meso-3,6-Dihydroxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane | 135352-30-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: meso-3,6-Dihydroxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane
• 英文别名: (2S*,3R*,6S*,7R*)-2,7-bis(tert-butyldimethylsilyloxymethyl)-2,3,6,7-tetrahydrooxepin-3,6-diol；(2S,3R,6S,7R)-2,7-bis[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3,6,7-tetrahydrooxepine-3,6-diol
• CAS: 135352-30-6
• 化学式: C₂₀H₄₂O₅Si₂
• 分子量: 418.721
• InChiKey: NZECSWDVFXGRJU-FZDBZEDMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.08
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  meso-3,6-Dihydroxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane 在 4-二甲氨基吡啶 、 sodium hydroxide 、 phosphate buffer 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 (2R,3S,6R,7S)-3-Acetoxy-6-hydroxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034
• 作为产物：
  描述：

  (1S,2S,5R,6R)-2,5-diiodo-9-oxabicyclo[4.2.1]nonan-7-one 在 Lindlar catalyst 、 焦磷酸硫胺素 咪唑 、 sodium hydroxide 、 sodium tetrahydroborate 、 sodium periodate 、 草酰氯 、 dimethyl sulfide borane 、 四丁基氟化铵 、 氢气 、 双氧水 、 氧气 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 106.0h， 生成 meso-3,6-Dihydroxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane
  参考文献：
  名称：

  针对微藻聚醚毒素的模型研究。立体选择性进入C 8氧杂环丁烷亚基

  摘要：

  研究了β-烷氧基取代的氧杂环丁烷的区域和立体定向合成的新合成策略，该策略涉及碘促进的9-氧代双环（6.1.0）non-4-en-2-one的环穿环扩展。使用单一的氧气加成将氧杂二烯进行立体控制的1,4-二加氧反应会转化为现有的取代基，然后使用Lindlar催化剂在甲醇中将生成的内过氧化物进行部分清洁的氢化，从而得到目标物质。

  DOI：

  10.1016/s0040-4039(00)79691-2

文献信息

• Enantioselective synthesis of the medium ring ethers, tetrahydrooxepin, oxocane and hexahydrooxonin, of ciguatoxin. Extensive ring-expansion and chemoenzymatic desymmetrization strategy
  作者：Tohru Oishi、Megumi Maruyama、Mitsuru Shoji、Kenji Maeda、Naomi Kumahara、Shin-ichiro Tanaka、Masahiro Hirama

  DOI：10.1016/s0040-4020(99)00370-1

  日期：1999.6

  The extensive ring-expansion strategy for the synthesis of tetrahydrooxepin, oxocane, and hexahydrooxonin, which correspond to the D(E), I and F rings of ciguatoxin (CTX1B, 1), respectively, has been established. Chemoenzymatic acylation of the meso alcohols using a lipase provides an expeditious entry for the enantiomeric building blocks. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations
  作者：Eleuterio Alvarez、Maria T. Diaz、Ricardo Perez、Jose L. Ravelo、Alicia Regueiro、Jose A. Vera、Dacil Zurita、Julio D. Martin

  DOI：10.1021/jo00089a034

  日期：1994.5

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.
• Model studies directed towards microalga polyether toxins. A stereoselective entry into C8 oxepane subunits
  作者：Eleuterio Alvarez、M.Teresa Díaz、Ricardo Pérez、Julio D. Martín

  DOI：10.1016/s0040-4039(00)79691-2

  日期：1991.5

  A new synthetic strategy for the regio and stereospecific synthesis of β-alkoxy-substituted oxepanes involving iodine promoted transannular ring expansion of 9-oxobicyclo (6.1.0) non-4-en-2-one was studied. Stereocontrolled 1,4-dioxygenation of oxepadienes using single oxygen addition occurs trans to the existing substituents and the resulting endoperoxides were cleanly partially hydrogenated using

  研究了β-烷氧基取代的氧杂环丁烷的区域和立体定向合成的新合成策略，该策略涉及碘促进的9-氧代双环（6.1.0）non-4-en-2-one的环穿环扩展。使用单一的氧气加成将氧杂二烯进行立体控制的1,4-二加氧反应会转化为现有的取代基，然后使用Lindlar催化剂在甲醇中将生成的内过氧化物进行部分清洁的氢化，从而得到目标物质。